CN105143425A

CN105143425A - Water-soluble film for delayed release

Info

Publication number: CN105143425A
Application number: CN201480015973.0A
Authority: CN
Inventors: 大卫·M·李; 尼古拉斯·塞斯; 詹妮弗·L·奇尔德斯; 斯蒂芬·布洛克
Original assignee: Monosol LLC
Current assignee: Monosol LLC
Priority date: 2013-03-15
Filing date: 2014-03-13
Publication date: 2015-12-09
Anticipated expiration: 2034-03-13
Also published as: MX346270B; KR101711455B1; JP2018030649A; JP2016520668A; AU2014236931A1; WO2014151718A2; AU2014236931B2; EP2970839B1; MX2015012296A; EP2970839A2; KR20150126411A; BR112015023216A2; CA2904373A1; CN105143425B; WO2014151718A3; BR112015023216B1; CA2904373C; JP6246891B2

Abstract

The disclosure provides a water-soluble film, including polyvinyl alcohol (PVOH) and (PVOH) and an acrylate resin (e.g., methyl acrylate), wherein the water-soluble film remains intact for at least 3 minutes when submerged in water heated to a temperature of about 40 DEG, as determined by Bleach Compatibility Method A (described herein). The disclosure further provides a packet or pouch comprising water-soluble film of the disclosure. The packet or pouch can optionally include two or more compartments. The disclosure further provides a pouch including a first sealed compartment containing a first composition, the first sealed compartment comprising the water-soluble film according to the disclosure. Optionally, the first composition can include a bleach composition.

Description

For the water-solubility membrane of delayed release

The cross reference of related application

Under 35U.S.C. § 119 (e), in the rights and interests of this No. 61/801,801, U.S. Provisional Patent Application requiring on March 15th, 2013 to submit to and its disclosure be incorporated herein by reference.

Technical field

Present disclosure is usually directed to water-solubility membrane.More particularly, present disclosure relates to for promoting agent the water-solubility membrane pouch of delayed release or bag from water-soluble pouch or bag.

Background technology

Water-soluble polymer films be typically used as wrapping material with simplify the material that will transmit dispersion, topple over, dissolve and dispensing.Such as, the bag manufactured by water-solubility membrane usually in order to pack home care compositions, such as, contains the pouch of laundry use or dish washing composition.Pouch can directly be added in the mixing vessel of such as bucket, tank or washing machine by human consumer.This advantageously provides accurate dispensing, eliminates the needs that human consumer measures composition simultaneously.This pouch also can reduce will with distribute analogous composition from container, the confusion that such as pouring liquid cloth-washing detergent is relevant from bottle.This pouch also makes the hand of composition wherein and user isolate.In a word, the soluble polymeric film bag comprising premeasuring reagent provides human consumer the convenience used in numerous applications.

If basic activated dose (such as, bleaching additive) introduces in the subordinate phase postponing such as 15-20 minute, then can increase effect of some laundry promoting agent (such as, enzyme).In order to realize the basic activated dose of delayed release in wash(ing)cycle, water-solubility membrane bag must slowly dissolve and keep substantially complete at nominal 40 DEG C and last 15-20 minute.Also must make the component mutual chemical of unitary dose bag system mutually perhaps mutual chemical isolation to prevent and any chemistry of packaging material or physical change.

Some water-soluble polymer films in order to manufacture bag will be dissolved by halves during this laundry wash cycle, film residue is stayed on the article in washings, or will dissolve prematurely, the effect causing may becoming unstable some laundry additive (such as, enzyme) under other promoting agents exist reduces.

Water-soluble polymer films based on PVOH can experience the change of dissolution characteristics.The known acetate group in copolymerization (vinyl acetate-ethylene alcohol) polymkeric substance of those skilled in the art will be hydrolyzed by acid or basic hydrolysis.This is just based on the intrinsic weakness in the application of the film of vinyl-acetic ester/alcohol co-polymer specific to business PVOH resin.Under the highly basic of such as laundry bleaching additive exists, the PVOH resin with position, side carboxyl of the methyl acrylate sodium salt resin of such as vinyl alcohol/hydrolysis will through the process deterioration in a few week under relatively hot (surrounding environment) and high humidity.

Therefore, think that this film can become more soluble due to the chemical interaction between the shelf lives between film and the alkaline compositions in pouch.Therefore, along with they are aging, bag can become in hot washing period (nominal 40 DEG C) period and more and more be tending towards dissolving prematurely, and can reduce effect of some laundry promoting agent due to the existence of SYNTHETIC OPTICAL WHITNER again.

For postpone relative to cloth-washing detergent to transmit SYNTHETIC OPTICAL WHITNER water-soluble/state of the art of reactivity/dispersed pouch and bag comprises the many compartment water-soluble pouches used by the manufacture of polyvinyl alcohol (PVOH) film, wherein the second pouch of holding solid is slower than the first packet dissolves, as at United States Patent (USP) 6,727, No. 215 with described in U.S. Patent Bulletin No. 2009/0011970 and No. 2010/0192086.In addition, the various different chemical coatings that the mode as delayed release is administered to the powder of SYNTHETIC OPTICAL WHITNER or bleach-activating agent are described in United States Patent (USP) 4,725, No. 378; 5,965, No. 505 and 5, in 755, No. 992.

Still need to have in the hot water required delayed release characteristic, enough solvabilities thus once complete do not have wash(ing)cycle any film residue to stay on wash load, with the chemistry of cloth-washing detergent and physical compatibility and the bag of water-solubility membrane of mechanical properties comprising good workability.

Summary of the invention

Present disclosure provides water-soluble pouch or the bag of the first sealed compartments comprising accommodation first composition, described first sealed compartments comprises water-solubility membrane, described water-solubility membrane comprises polyvinyl alcohol (PVOH) and acrylate resin (such as, methyl acrylate) and described first composition comprises alkaline reagents.Optionally, as by bleach-compatible method A (described herein) measure, keep complete at least 3 minutes when described water-solubility membrane is in the water being immersed in the temperature being heated to about 40 DEG C, and after this dissolve completely.Optionally, described alkaline reagents can comprise whitener composition.In addition optionally, described whitener composition usable paint coating.Described bag or pouch optionally comprise two or more compartment.

In a related aspect, present disclosure provides water soluble resin and preparation according to selecting to comprise PVOH and methyl acrylate to have the step manufacture of the water-solubility membrane of the thickness of about 3 mil-Yue 6 mils (about 0.076mm-is about 0.15mm) for postponing the method for the film dissolved in the hot water; Wherein said water soluble resin comprises the methyl acrylate of about 5 % by mole.

In one embodiment, described handbag draws together the first sealed compartments and the second sealed compartments.Described second compartment and described first sealed compartments are in usually stacked relation, make described second sealed compartments and described first sealed compartments share the partition wall of described internal pouch.

In one embodiment, the described bag comprising the first compartment and the second compartment also comprises the 3rd sealed compartments.Described 3rd sealed compartments and described first sealed compartments are in usually stacked relation, make described 3rd sealed compartments and described first sealed compartments share the partition wall of described internal pouch.

In some embodiments, described first composition and described second composition are individually selected from liquid and powder.Such as, described embodiment can comprise following combination: liquid, liquid; Liquid, powder; Powder, powder; With powder, liquid.

In some embodiments, described first composition, the second composition and the 3rd composition are individually selected from liquid and powder.Such as, described embodiment can comprise following combination: solid, liquid, liquid; Solid, solid, liquid; With liquid, liquid, liquid.

In in the embodiment described in which any one, described single compartment or multiple sealed compartments hold composition.Described multiple compartment can hold identical or different composition separately.Described composition is selected from liquid, solid or its combination." liquid " used herein comprises paste, liquid, gel, foams or mousse.The limiting examples of liquid comprises light-duty and heavy duty liquid detergent composition, fabric intensifier, the detergent gels being generally used for laundry, SYNTHETIC OPTICAL WHITNER and laundry additive.The gas of such as suspended bubble or the solid of such as particle can be included in described liquid." solid " used herein comprises powder, coacervate or its mixture.The limiting examples of solid comprises: micro-capsule; Bead; Bar; With pearly-lustre ball.The solid of such as one or more solids compositions can provide the process benefit including but not limited to thorough washing (through-the-wash) benefit, pre-treatment benefit and/or effect attractive in appearance.

In in the embodiment described in which any one, described composition can be selected from liquid light type and liquid heavy duty liquid detergent composition, powder detergent composition, fabric intensifier, be generally used for the detergent gels of doing washing and SYNTHETIC OPTICAL WHITNER and laundry additive.

According to the review of following detailed description, by reference to the accompanying drawings, those of ordinary skill in the art is by obviously other aspect and advantage.Although composition as herein described, film, pouch and bag are allowed for the embodiment of various ways, but hereafter describe and comprise specific embodiments, it is illustrative for should understanding its disclosure, and does not expect and make the present invention be limited to specific embodiments described herein.

Such as the optional feature of concrete component, its compositing range, substituting group, condition and method steps can be selected from various embodiment provided herein.

Accompanying drawing explanation

In order to promote the understanding of present disclosure further, enclose four figure at this, wherein:

Fig. 1 is the skeleton view in order to measure the water disintegration of membrane sample and the testing installation of dissolution time according to MSTM205 as herein described;

Fig. 2 illustrates the testing installation of water miscible program and the skeleton view of test mechanism that measure membrane sample according to MSTM205 as herein described;

Fig. 3 is the vertical view of the test mechanism of Fig. 2; And

Fig. 4 is the chart of pH to the time of following lozenge: the 10g compressing tablet of sodium carbonate and SPC-D (1:1 % by weight), be coated with polyoxyethylene glycol (PEGMW6,000) the 10g compressing tablet of sodium carbonate and SPC-D (1:1 % by weight), be contained according to the 10g compressing tablet of the sodium carbonate in water-solubility membrane pouch of the present invention and SPC-D (1:1 % by weight) and be coated with PEG (MW6,000) and be contained in the 10g compressing tablet according to the sodium carbonate in water-solubility membrane pouch of the present invention and SPC-D (1:1 % by weight).

Embodiment

Present disclosure provides water-soluble pouch or the bag of the first sealed compartments comprising accommodation first composition, described first sealed compartments comprises the wall of water-solubility membrane, and described water-solubility membrane comprises polyvinyl alcohol (PVOH) and acrylate resin and described first composition comprises alkaline reagents.Preferred described film is unitary film.Described compartment can have the whole wall provided by the film based on PVOH.In the embodiment of any type as herein described, described acrylate resin can be methyl acrylate.Example as the election, in the embodiment of any type as herein described, this acrylate resin can be methyl acrylate or methyl methacrylate.Optionally, as by bleach-compatible method A (described herein) measure, keep complete at least 3 minutes when this water-solubility membrane is in the water being immersed in the temperature being heated to about 40 DEG C, and after this dissolve completely.Optionally, described alkaline reagents can comprise whitener composition.In addition optionally, this whitener composition usable paint coating.This bag or pouch can optionally comprise two or more compartment.In addition or for selecting in example, as by bleach-compatible method B (described herein) measure, the water-solubility membrane comprising polyvinyl alcohol (PVOH) and methacrylate resin keeps complete at least 9 minutes in washing machine at 40 DEG C, and after this dissolves completely.Advantageously, the water-solubility membrane of present disclosure can be used for postponing alkaline SYNTHETIC OPTICAL WHITNER and is discharged in wash(ing)cycle, postpones the alkalization of washing water thus and is reduced in the loss function of the alkaline-sensitive material existed in cloth-washing detergent.

Unless otherwise stated, expect these goods and method comprise hereafter further describe in addition optional key element, one or more any combination in characteristic sum step (be included in shown in figure those) embodiment.

Term used herein " comprise " instruction except specify those except, the potentiality of other reagent, element, step or feature comprises.

Advantageously, time when bleaching components coating as described herein and in the pouch being encapsulated in the water-solubility membrane comprising present disclosure, as measured by bleach-compatible method A, keep complete at least 8 minutes when water-solubility membrane is in the water being immersed in the temperature being heated to about 40 DEG C, correspond to and keep complete at least 15 minutes as being determined in washing machine by bleach-compatible method B.Therefore, water-solubility membrane/SYNTHETIC OPTICAL WHITNER the coating of present disclosure can be used for making alkaline SYNTHETIC OPTICAL WHITNER at least 15 minutes hang-over n.s of wash(ing)cycle, postpone the alkalization of water thus and prevent the loss function of the alkaline-sensitive material (such as, enzyme) existed in cloth-washing detergent.

In one embodiment, described handbag draws together the first sealed compartments and the second sealed compartments.Described second compartment and described first sealed compartments can be in usually stacked relation, make described second sealed compartments and described first sealed compartments share the partition wall of described internal pouch.

In one embodiment, the described bag comprising the first compartment and the second compartment also comprises the 3rd sealed compartments.Described 3rd sealed compartments and described first sealed compartments can be in usually stacked relation, make described 3rd sealed compartments and described first sealed compartments share the partition wall of described internal pouch.

In some embodiments, described first composition, described second composition and described 3rd composition are individually selected from liquid and solid.Such as, described embodiment can comprise following combination: solid, liquid, liquid; Solid, solid, liquid; With liquid, liquid, liquid.

In in the embodiment described in which any one, described single compartment or multiple sealed compartments hold composition.Described multiple compartment can hold identical or different composition separately.Described composition can be selected from liquid, solid or its combination." liquid " used herein comprises free-pouring liquid and paste, gel, foams and mousse.The limiting examples of liquid comprises light-duty and heavy duty liquid detergent composition, fabric intensifier, the detergent gels being generally used for laundry, SYNTHETIC OPTICAL WHITNER and laundry additive.The gas of such as suspended bubble or the solid of such as particle can be included in described liquid." solid " used herein includes but not limited to powder, coacervate and composition thereof.The limiting examples of solid comprises: micro-capsule; Bead; Bar; With pearly-lustre ball.Solids composition can provide the process benefit including but not limited to thoroughly wash benefit, pre-treatment benefit and/or effect attractive in appearance.

Such as, in any one in washing emporium embodiment, described composition can be selected from liquid light type and liquid heavy duty liquid detergent composition, powder detergent composition, fabric intensifier, be generally used for the detergent gels of doing washing and SYNTHETIC OPTICAL WHITNER and laundry additive.

As used herein and unless otherwise, otherwise all measurements of PVOH viscosity (centipoise (cP)) are all in 4% (w/v) aqueous solution at 20 DEG C, and unless otherwise, otherwise all measurements of carboxymethyl cellulose viscosity are all in 2% (w/v) aqueous solution at 25 DEG C.

As used herein and unless otherwise, otherwise term " % by weight (wt.%) " and " % by weight (wt%) " mean with " drying " of the weighing scale of whole film (non-water) part (as applicable) or with the composition of the qualification key element of the part (as applicable) of the weighing scale being encapsulated in the whole composition in pouch.As used herein and unless otherwise, otherwise term " phr " means the composition of the qualification key element number of each hundred parts water-soluble PVOH resins.

As used herein and unless otherwise, otherwise term " disintegration " refers to whole inclusion of water-soluble pouch release pouch and point that film does not dissolve.

As used herein and unless otherwise, otherwise term " dissolving " refers to that film and any rest segment thereof are dissolved completely and be in the point in solution.

As used herein and unless otherwise, otherwise term " not enough solvability " refer to film be heated to 40 DEG C temperature water in do not dissolve completely in 55 minutes or shorter time.

As used herein and unless otherwise, otherwise term " some A time " refers to that the pH of solution in bleach-compatible method A starts the point risen with the speed that per minute is more than or equal to 0.1pH unit.

Polyvinyl alcohol (PVOH) is comprised according to the water-solubility membrane of present disclosure.PVOH is the usual synthetic resins prepared by the alcoholysis being commonly referred to hydrolysis or saponification of polyvinyl acetate.The PVOH that nearly all acetate group has all changed into the complete hydrolysis of alcohol radical is the polymkeric substance of the highly crystalline of strong hydrogen bonding bonding, and it is only dissolved in the hot water being greater than about 140 ℉ (60 DEG C).If allow the acetate group retaining enough numbers after polyvinyl acetate Ester hydrolysis, then PVOH polymkeric substance to be called partial hydrolysis, it is more weak hydrogen-bonded and compared with low degree crystallization, and dissolves in the cold water being less than about 50 ℉ (10 DEG C).Middle cold/hot water dissolvable film can comprise the PVOH (such as, degree of hydrolysis is about 94%-about 98%) of the partial hydrolysis such as, and only can easily be dissolved in warm water, such as, dissolve rapidly under about 40 DEG C or higher temperature.PVOH type that is complete and partial hydrolysis is commonly called PVOH homopolymer, and just partial hydrolysis type is vinyl alcohol-vinyl acetate multipolymer academicly.Therefore, the multipolymer with acrylate can be vinyl alcohol-vinyl acetate trimer.

The viscosity of resin well known in the art and the weight average molecular weight of this resin relevant, and viscosity is commonly used for substitute.The viscosity of PVOH resin measures by using the solution of BrookfieldLV type viscometer as measured fresh preparation described in BritishStandardENISO15023-2:2006AnnexEBrookfieldTest method with UL tube stub.

As mentioned above, the acetate group in copolymerization (vinyl acetate-ethylene alcohol) polymkeric substance is hydrolyzed by acid or basic hydrolysis.Therefore, the dissolubility property of the bag formed with PVOH in the appropriate case can be deteriorated in time, and therefore bag may dissolve prematurely.

Have been found that the solubleness of film in 40 DEG C of water comprising consoluet PVOH (that is, degree of hydrolysis is 98-100%) homopolymer depends on the molecular weight of PVOH as illustrated by an embodiment.Such as, the film comprising the PVOH homopolymer (its medium viscosity is about 4cPs or less) of low-molecular-weight complete hydrolysis dissolves completely at 40 DEG C.The film of the PVOH homopolymer of the complete hydrolysis that the viscosity comprising to be greater than 10cPs is feature does not dissolve and comprises and at 40 DEG C, inconsistent solvability is described with the film of the PVOH homopolymer of the viscosity of the about 5-6cPs complete hydrolysis that is feature at 40 DEG C.Also find to dissolve at 40 DEG C (namely with comparatively low viscosity for feature and therefore there is relatively small molecular weight) the PVOH homopolymer of complete hydrolysis be difficult to processing and gained film has poor mechanical properties.

In addition, have been found that as illustrated in an embodiment, the solubleness of film in 40 DEG C of water comprising the PVOH homopolymer of partial hydrolysis depends on the pH of water.Under neutral ph, the film comprising the PVOH homopolymer of partial hydrolysis is dissolved in the water completely at 40 DEG C.But when with alkaline reagents (such as, sodium carbonate and SPC-D) contact test, at 40 DEG C, film becomes water insoluble.When not wanting bound by theory, thinking that sodium carbonate is hydrolyzed this resin further, producing the homopolymer of complete hydrolysis, shown that it is water insoluble at 40 DEG C.This interaction makes the PVOH homopolymer of partial hydrolysis be not suitable for separately for packing in the film of the basic component of the bleaching component comprising such as sodium carbonate or SPC-D because dissolving is discharged in the wash water system at 40 DEG C.

The PVOH resin of present disclosure illustrates good processing characteristics, and comprises film solubilized at 40 DEG C of the PVOH resin of present disclosure, even when contacting with the 1:1 mixture of SPC-D with sodium carbonate.The PVOH resin of present disclosure is the multipolymer comprising PVOH and acrylate.

The PVOH comprised in multipolymer in the water-solubility membrane being used in present disclosure can be (that is, degree of hydrolysis is about 98%-about 100%) of complete hydrolysis, has few residual acetate groups.Along with degree of hydrolysis is reduced to lower than complete hydrolysis, will the physical strength of reduction be had by the film of this resin manufacture, but dissolve quickly.Certainly, as known in the art, when degree of hydrolysis lower than about 60%, PVOH resin and by its manufacture film will be no longer water-soluble.

Multipolymer of the present invention can comprise the acrylate of the such as methyl acrylate and/or methyl methacrylate of about 5 % by mole.When not wanting bound by theory, think that position, the side carboxyl experience methanolysis of acrylate is to form lactonic ring.Think, form the PVOH of complete hydrolysis because the lactonic ring closed does not experience hydrolysis, even if so solubilized at resin also remains on 40 DEG C under sodium carbonate exists.As shown in Example, along with such as methyl methacrylate in the copolymer acrylate % by mole to be reduced to lower than 5%, PVOH copolymer resin be heated to about 40 DEG C temperature water in solubleness reduce.Think that solubleness reduces owing to the amount due to PVOH in the copolymer increases and makes this resin similar more nearly to the PVOH polymkeric substance of complete hydrolysis.In addition, think % by mole to be increased to higher than 5 % by mole along with acrylate in the copolymer because this polymkeric substance becomes only be dissolvable in water more and more hotter water, so PVOH copolymer resin be heated to about 40 DEG C temperature water in solubleness reduce.

In acrylate-PVOH multipolymer, the amount of acrylate resin can in order to affect the water-solubility membrane that comprise acrylate-PVOH multipolymer and the solvability of bag manufactured by water-solubility membrane, and therefore delayed release characteristic.Such as, comprise the bag being included in water soluble resin the water-solubility membrane being greater than about 5 % by mole of acrylate will illustrate at the temperature lower than the bag comprising the water-solubility membrane being included in about 5 % by mole of acrylate in water soluble resin for the similar delayed release length of the inclusion be encapsulated in bag.In addition, comprise the bag being included in water soluble resin the water-solubility membrane being less than about 5 % by mole of acrylate will illustrate at the temperature higher than the bag comprising the water-solubility membrane being included in about 5 % by mole of acrylate in water soluble resin for the similar delayed release length of the inclusion be encapsulated in bag.The amount of the acrylate comprised in water-soluble PVOH multipolymer can be about 2 % by mole of-Yue 10 % by mole, about 2 % by mole of-Yue 8 % by mole, about 2 % by mole-Yue 6 % by mole, about 3 % by mole-Yue 6 % by mole, about 4 % by mole-Yue 6 % by mole and/or about 5 % by mole.

Described water soluble resin can any appropriate amount of amount such as in following scope be included in described water-solubility membrane: about 35 % by weight-Yue 90 % by weight, or about 40 % by weight-Yue 90 % by weight, or about 45 % by weight-Yue 90 % by weight, or about 50 % by weight-Yue 90 % by weight, or about 55 % by weight-Yue 90 % by weight, or about 60 % by weight-Yue 90 % by weight, or about 65 % by weight-Yue 90 % by weight, or about 70 % by weight-Yue 90 % by weight, or about 75 % by weight-Yue 85 % by weight, or about 80 % by weight.

For the water-soluble PVOH resin in film as herein described can for the suitable any viscosity of required film character, being preferably about 40.0cP or about 10.0cP-at about 8.0-, to be about 30cP or the about 13cP-viscosity be about in the scope of 27cP be feature.

Can comprise such as to be applicable to other optional additive components of the amount of its desired use according to the water-solubility membrane of present disclosure, include but not limited to softening agent, tensio-active agent, emulsifying agent, filler, extender, anti-hard caking agent, release agent, defoamer, membrane-forming agent and other functional components.

Water is considered to the very effective softening agent of PVOH and other polymkeric substance; But the volatility of water makes its compromised utility, because polymeric film must have at least certain intensity (steadiness) for the multiple environmental conditions comprising low and high relative humidity.Glycerol has the volatility more much lower than water and effective softening agent as PVOH and other polymkeric substance is in use for a long time.If the usage level in film preparation is too high, glycerol or other such liquid plasticizers can cause surface " perspiration " and greasy individually.If perspire not such as surperficial dusting and alleviating in some way, then this can cause the problem in film, such as the unacceptable feel of human consumer and even film in roller or the stacking middle blocking of sheet.This can be characterized by super plasticising (overplasticization).Such as, but if be added in film by softening agent very little, for many end-uses, change into the final utilization form such as wrapped, this film can lack enough ductility and pliability.

The softening agent used in the water-solubility membrane of present disclosure includes but not limited to Sorbitol Powder, glycerine, two glycerine, propylene glycol, ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, the polyoxyethylene glycol up to MW400,2-methyl isophthalic acid, ammediol, lactic acid, glyceryl monoacetate, vanay, triethyl citrate, 1,3 butylene glycol, TriMethylolPropane(TMP) (TMP), polyether triol and combination thereof.When using less softening agent, this film can become more crisp, and when using more softening agent, this film can lose tensile strength.Softening agent such as can be about 50phr or about 10phr-at about 10phr-and be about the amount that 40phr or about 15phr-is about within the scope of 30phr and be included in water-solubility membrane.

The tensio-active agent used in water-solubility membrane is well known in the art.Optionally comprise tensio-active agent to help resin solution dispersion after casting.The suitable surfactant of the water-solubility membrane of present disclosure includes but not limited to dialkyl sulfosuccinate, the Lactated fatty acid ester of glycerine and propylene glycol, lipid acid lactoyl ester, sodium alkyl sulfate, polysorbate20, polysorbate60, polysorbate65, polysorbate80, alkyl polyglycol ether, Yelkin TTS, the acetylated fatty acid esters of glycerine and propylene glycol, Sodium Lauryl Sulphate BP/USP, the acetylize ester of lipid acid, mnyristoyl dimethyl amine, trimethylammonium ox ester alkyl ammonium chloride, quaternary ammonium compound, its salt and aforesaid any combination.Tensio-active agent very little can cause film to have hole sometimes, and too many tensio-active agent can cause film to have greasy or unctuousness due to the excess surface active agent existed on the surface of the film.Therefore, tensio-active agent such as can be less than about 2phr, such as be less than about lphr or the amount that is less than about 0.5phr is included in water-solubility membrane.

In film-forming composition, expect that the class second component used is defoamer.Defoamer can help the coalescent of foam bubbles.For including but not limited to hydrophobic silica silicon according to the suitable defoamer in the water-solubility membrane of present disclosure, such as, with the silicon-dioxide of fine particle size or fumed silica, comprise the Foam that can derive from EmeraldPerformanceMaterials defoamer, comprises Foam 327, Foam uVD, Foam 163, Foam 269, Foam 338, Foam 290, Foam 332, Foam 349, Foam 550 and Foam 339, they are patented non-mineral oil defoamer.In embodiments, defoamer can 0.7phr or less, such as 0.5phr, 0.05phr, 0.04phr, 0.03phr, 0.02phr or 0.01phr amount use.

Proper lubrication agent/releasing agent can include but not limited to lipid acid and salt, fatty alcohol, fatty acid ester, aliphatic amide, fatty amine acetates and fatty amide.Preferred lubricants/release agents is lipid acid, soap and fatty amine acetates.In embodiments, lubricants/release agents can the amount of such as about 0.02 % by weight-Yue 1.5 % by weight, optional about 0.1 % by weight-Yue 1 % by weight use.

Suitable filler/extender/anti-hard caking agent/release agent includes but not limited to starch, treated starch, crosslinked polyvinylpyrrolidone, crosslinked Mierocrystalline cellulose, Microcrystalline Cellulose, silicon oxide, metal oxide, calcium carbonate, talcum powder and mica.Preferred material is starch, treated starch and silicon oxide.In a class embodiment, in water-solubility membrane, the amount of filler/extender/anti-hard caking agent/release agent is such as in the scope of about 1 % by weight-Yue 6 % by weight or about 1 % by weight-Yue 4 % by weight or about 2 % by weight-Yue 4 % by weight.

During the preparation of PVOH resin solution, brown effect may be there is.And in most applications, need transparent and colourless water-solubility membrane, suitable SYNTHETIC OPTICAL WHITNER can be added in PVOH resin solution.Have been found that, when using with the amount of about 0.05 % by weight-Yue 1.0 % by weight or about 0.05 % by weight-Yue 0.7 % by weight or about 0.1 % by weight-Yue 0.5 % by weight or about 0.1 % by weight-Yue 0.3 % by weight or about 0.2 % by weight in the composition, sodium metabisulfite is used obviously to maintain the transparency of during preparation solution and colourless property.

The thickness of water-solubility membrane also can in order to the solvability of the bag that affects water-solubility membrane and manufactured by water-solubility membrane and delayed release characteristic.Along with the thickness of water-solubility membrane increases, the dissolution time of water-solubility membrane increases.The water-solubility membrane of present disclosure can have the thickness of about 3 mil-Yue 6 mils (about 0.076mm-is about 0.15mm), such as about 3.5 mil-Yue 6 mils (about 0.09mm-is about 0.15mm) or about .4 mil-Yue 5.5 mil (about 0.10mm-is about 0.14mm) or about 4.5 mil-Yue 5.5mil (0.11mm-is about 0.14mm) or about 5 mils (0.13).

The advantage of the water-solubility membrane of present disclosure is, after in the water being immersed in the temperature being heated to 40 DEG C, when contacting with the 1:1 mixture of SPC-D with sodium carbonate, as by bleach-compatible method A measure, they can keep complete at least about 3 minutes, or as by bleach-compatible method B measure, they can keep complete at least 9 minutes.

Bleach-compatible method A is can in order to measure the water-solubility membrane laboratory test whether compatible with the alkaline reagents of such as SYNTHETIC OPTICAL WHITNER.Test sample for method A is to fill with the compressing tablet of 5.8g1:1 (% by weight) sodium carbonate and SPC-D mixed powder or 10g same material and with the little 2x2 inch (5.08x5.08cm) of post heat-seal, the water-solubility membrane pouch of nominal 5 mil (127 μm).SYNTHETIC OPTICAL WHITNER lozenge can comprise the stearic acid as tackiness agent and manufacture by compress technique well-known to those having ordinary skill in the art.Chlorinated lime material is buied from SolvayChemicals.This pouch uses 0.5 inch of (1.3cm) metal cylinder mould of ethenoid resin coating fastening and to be immersed in the 600ml beaker containing 500ml40 DEG C of deionized water and to stir.Comprise the metal cylinder mould of pouch in submergence before, water is made to be stabilized to pH7.After by pouch submergence, use the pH of pH probe monitoring water and per minute record, until reach the pH of 9.5 or higher, or until 20 minutes in the past.Observe and record integrity and the solubility behavior of pouch.

Sharply mark is increased to discharge via active material the pH caused at about 9-from pouch within the scope of about 12 minutes from on-test with the desirable solubility behavior of the water-solubility membrane of the alkaline bleaching agent contact in 40 DEG C of water.This ideal behavior correspond within the commercial laundry machine cycle in nominal 40 DEG C of washing water the actives hang-over n. be about 15-20 minute (bleach-compatible method B).

Bleach-compatible method B tests the water-soluble solubility behavior wrapped in commercial laundry machine prepared by the water-solubility membrane of encapsulating SYNTHETIC OPTICAL WHITNER.Test sample is as prepared for as described in method A above.Sample is service routine Koch/Bunt (cotton/painted) or equivalent test in SIEMENS board S16-79 washing machine.SIEMENS board S16-79 automatic washing machine has 65 liters of drum capacities and variable thermal creep stress.The temperature of washing water is 20 DEG C, 40 DEG C or 60 DEG C.In the test reported herein, water hardness measuring is 250ppmCaCO ₃(14 ° of d, the Deutschland hardness number of degrees).Wash load is 3kg, is made up of 2 coverlets (1.5x1.5mISO2267), 4 pillowcases (0.8x0.8mISO2267) and 3 diablement fort towels bleached.The dissolution time of method B corresponds to as by reaching the time of the pH of 9.5 or higher measured by pH probe.In a class embodiment, required behavior sharply increases to mark to use nominal 40 DEG C of washing water within the commercially available automatic washing machine cycle via discharging from pouch the pH caused at about 15-20 minute active material.

A kind ofly expect the embodiment of kind with the good hot-forming property of the water-solubility membrane of manufacture as described herein for feature.The film of thermoformable is can via using heat and power and shaping film.

Film is thermoformed into following process: heating film, make it such as shaping in a mold and subsequently allow film cooling, therefore film will keep be shaped shape, the shape of such as mould.This heat can make to use in any suitable manner.Such as, before being fed on the surface by film or once from the teeth outwards, then film passes through under a heating element by making it or passes warm air direct heating.For the election, it such as can be administered to indirect heating on film by heating surface or by hot object.In some embodiments, this film uses infrared light heating.This film can be heated to the temperature of about 50 DEG C of-Yue 150 DEG C, about 50 DEG C of-Yue 120 DEG C, about 60 DEG C-Yue, 130 DEG C, about 70 DEG C-Yue 120 DEG C or about 60 DEG C-Yue 90.Thermoforming is undertaken by any one or more in such as following technique: manual drape thermal softening film is on mould, or softening film in a mold pressure bring out shaping (such as, vacuum forming), the fresh sheet material automatic high speed index of extruding that maybe will have an accurate known temperature is to shaping and deburring station, or film is automatically put, blocked and/or pneumatic stretching and pressure forming.The degree that film stretches is defined by region stretch ratio, and region stretch ratio is that bag (or cavity) surface-area is divided by the film surface-area before thermoforming.Region stretch ratio (also referred to as region stretching depth) can according to technologyofThermoforming (is hot pressed into shape technology), JamesL.Throne, Hanserpublisher, (1996) the 7.4th chapters, the method described in 488-494 page (ISBN3-446-17812-0) calculates.In this article, for thermoforming film, region stretch ratio can within the scope of 1.05-2.7; Or within the scope of 1.2-2.3; Or within the scope of 1.3-2.0.

As heating for choosing or in addition to heating, before film is fed on the surface or once from the teeth outwards, film soaks by any suitable mode, such as directly soaked to film by spraying wetting agent (comprising water, the solution of film composition, the softening agent of film composition or aforesaid any combination), or indirectly soak by wetted surface or by using on wet mass body to film.

Once film has been heated and/or soaked, it just can preferably use vacuum to be stretched in suitable mould.The filling of molded film realizes in any suitable manner by profit.In some embodiments, most preferred method will depend on the form of product and required filling speed.In some embodiments, molded film is filled by online filling technique.Subsequently by any suitable method, use the second film the open encapsulating of filling to be closed, thus form pouch.This can be horizontal with continuous constant motion while complete.Close by following realization: above open bag and on charging second film, preferably water soluble film continuously, and subsequently preferably in usual region between mould and therefore between bag, by the first film together with the second film phonograph seal.Described packaging is formed and sealing method is known in the art.

Any suitable method of sealed packet and/or its single compartment can be utilized.The limiting examples of these class methods comprises heat-sealing, solvent welding, solvent seal or fluid-tight and combination thereof.Usually, region heat or the solvent treatment of sealing will only be formed.Heat or solvent are applied on closed material usually by any method, and are usually only applied on the region of formation sealing.If use solvent seal or fluid-tight or welding, then preferably also can use heat.Preferred fluid-tight or solvent seal/welding process comprise on the region that solvent selectivity to be administered between mould, or on closed material, by such as this being sprayed or being printed onto on these regions, and subsequently pressure is applied on these regions, to form sealing.Such as, sealed roller as above and band (heat is optionally also provided) can be used.

The pouch be shaped cuts by cutting unit subsequently.Cutting can use any known method to realize.Preferably can cut and also carry out in a continuous manner, and preferably use constant speed and preferably carry out while being horizontal.Cutting unit can be such as sharp objects or hot object or laser, thus in the later case, hot object or laser ' burn ' wear film/sealing area.

The different compartments of many compartment pouchs can mode be manufactured in together shoulder to shoulder, and the pouch of the wherein combination of gained is by cutting and separating or be not separated.For the election, compartment can manufacture individually.

In embodiments, pouch can according to the method manufacture comprised the following steps:

A) the first compartment (such as, described above) is formed;

B) be formed in the enclosed compartment formed in step (a) some or all in recess, to produce the second molding compartment stacked on the first compartment;

C) fill by means of tertiary membrane and close the second compartment;

D) the first film, the second film and tertiary membrane is sealed; With

E) film is cut, to generate many compartment pouchs.

The recess formed in step (b) is by realizing the compartment application of vacuum of preparation in step (a).

In some embodiments, one or more second and/or the 3rd compartment can manufacture in a separate step, and combine with the first compartment subsequently, as described in No. 08101442.5, european patent application or WO2009/152031 (on June 13rd, 2008 submits to and transfers Procter & GambleCompany).

In some embodiments, pouch can according to the method manufacture comprised the following steps:

A) be used in the first film on the first forming machine, optional use heat and/or vacuum, form the first compartment;

B) the first compartment is filled with the first composition;

C) on the second forming machine, optional use heat and vacuum, make the second film distortion, to manufacture the second molding compartment and the 3rd optional molding compartment;

D) the second compartment and the 3rd optional compartment is filled;

E) tertiary membrane is used to seal the second compartment and the 3rd optional compartment;

F) the second compartment of sealing and the 3rd optional compartment are placed on the first compartment;

G) the first compartment, the second compartment and the 3rd optional compartment is sealed; With

H) film is cut, to generate many compartment pouchs.

The suitability that first forming machine and the second forming machine can carry out said process based on it is selected.In some embodiments, the first forming machine can be horizontal form machine, and the second forming machine can be drum forming machine, such as, be positioned on the first forming machine.

Being to be understood that by using suitable feed station, may can producing many compartment pouchs, thus be incorporated to the composition of many differences or uniqueness and/or different or unique liquid, gel or paste composition.

Pouch of the present invention can hold multiple combination thing.Many compartment pouchs can hold identical or different composition in each independent compartment.

As mentioned above, the film of present disclosure and pouch is specific is advantageously used in packaging (such as, directly contacting) basic material.

This feature of present disclosure can in order to keep composition physical sepn or the distribution each other containing incompatible composition (such as, SYNTHETIC OPTICAL WHITNER and enzyme).Think such this constituents of distribution easily extensible work-ing life and/or reduce physical instability.In addition or for the election, such distribution can provide cosmetic benefits, as described in No. 09161692.0, european patent application (on June 2nd, 2009 submits to and transfers Procter & GambleCompany).

After in the water being immersed in the temperature being heated to 40 DEG C, when contacting with the 1:1 mixture of SPC-D with sodium carbonate, as by bleach-compatible method A measure, the release of the alkaline reagents of such as sodium carbonate or SPC-D SYNTHETIC OPTICAL WHITNER is advantageously postponed at least about 3 minutes by the pouch of the film manufacture according to present disclosure, or as by bleach-compatible method B measure, postpone its release at least 9 minutes.

Pouch can comprise one or more alkaline reagentss comprising inorganic bleaching agents.When not wanting bound by theory, thinking that the inorganic bleaching agents comprising sodium carbonate and/or SPC-D under water or high humidity exist will make the deterioration of PVOH film, increasing the solvability of PVOH film thus.But according in the film of present disclosure, think, owing to there is the lactonic ring from the methyl acrylate of about 5 % by mole in resin, this film is than the deteriorating effect of the more resistance to sodium carbonate of PVOH homopolymer and/or SPC-D.Such as other inorganic bleaching agents other alkaline reagentss by make in the mode identical with sodium carbonate and/or SPC-D PVOH film deterioration time, the release of this kind of alkaline reagents will be effectively postponed still consoluet while according to the film of present disclosure, for the same reason, this film effectively postpones the release of sodium carbonate and/or SPC-D.

Suitable inorganic SYNTHETIC OPTICAL WHITNER for this delayed release film comprises following salt: carbonate, borate, phosphoric acid salt, vitriol and silicate; And perhydrate salt, such as perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic bleaching agents is generally an alkali metal salt.Inorganic bleaching agents can be used as does not have Additional Protection, such as do not have physical protection to comprise as the crystalline solid of the coating on solids or around solid reunion block.For the election, inorganic bleaching agents can coating as described herein or encapsulate in addition.

In some embodiments of present disclosure, inorganic bleaching agents is with coated form.One of function of coating material is stop SYNTHETIC OPTICAL WHITNER and form the chemical interaction encapsulating the water-solubility membrane of the pouch of SYNTHETIC OPTICAL WHITNER, does not have for the water-solubility membrane pouch of cated SYNTHETIC OPTICAL WHITNER by extending the delayed release that water-solubility membrane will keep complete time quantum to strengthen SYNTHETIC OPTICAL WHITNER after being immersed in 40 DEG C of water thus relative to encapsulating.

Have been found that, illustrated by an embodiment, with laminate or in addition PVOH internal layer coating water-solubility membrane instead of coating SYNTHETIC OPTICAL WHITNER do not stop the interaction of causticity actives and outer membrane, and therefore do not provide and equal pouch or bag adds the pouch of the water-solubility membrane of the present invention of the thickness of the thickness of superimposed layer or the delayed release of Bao Eryan enhancing relative to having.

Have been found that as illustrated by an embodiment in addition, the SYNTHETIC OPTICAL WHITNER coating be made up of the N-80PolyOx of polyethylene oxide as DuPont is very ineffective in the chemical interaction stoping causticity actives and water-solubility membrane.In addition, discovery cmc coating is also not exclusively dissolved in water and is not therefore desirable coating material for desired use at 40 DEG C.

Inorganic bleaching agents is encapsulated in the embodiment in the water-soluble pouch of the water-solubility membrane comprising present disclosure herein and/or bag with the suitable paint of present disclosure herein wherein, as by bleach-compatible method A measure, described bag realizes inorganic bleaching agents at least about the delayed release of 8 minutes, or as by bleach-compatible method B measure, described bag realizes inorganic bleaching agents at least about the delayed release of 15 minutes.SYNTHETIC OPTICAL WHITNER coating material can comprise polyoxyethylene glycol (PEG) coating.Be applicable to any polyoxyethylene glycol that can be the molecular weight (dalton) had in following scope according to the polyoxyethylene glycol of the coating material of present disclosure: about 1000-about 20,000 or about 1000-about 18000 or about 1000-about 15000 or about 1000-about 11,000 or about 2000-about 10000 or about 3000-about 9000 or about 4000-about 8000 or about 5000-about 7000 or about 6000.Thickness according to the PEG coating of present disclosure can have in following scope: about 20 mil-Yue 150 mils (about 0.5mm-is about 3.8mm), about 20 mil-Yue 100 mils (about 0.5mm-is about 2.5mm), about 20 mil-Yue 80 mils (about 0.5mm-is about 2.0mm) or about 40 mil-Yue 60 mils (about 1.0mm-is about 1.5mm).

Before SYNTHETIC OPTICAL WHITNER compressing tablet is encapsulated in water-soluble pouch or bag, PEG can be coated on SYNTHETIC OPTICAL WHITNER compressing tablet.Such as, PEG coating is used by soaking replacing in the melting PEG of side everywhere at the temperature of about 65 DEG C of-Yue 67 DEG C of SYNTHETIC OPTICAL WHITNER compressing tablet successively.Lozenge is subsequently by be dipped in liquid nitrogen several seconds and to cool immediately by the lozenge of coating.Repeat to soak lozenge and soak lozenge to the process in liquid nitrogen in melting PEG, then, until the even coating thickness needed for obtaining.

For the election, comprising the first water-soluble bag of inorganic bleaching agents or pouch can with scleroma pied-de-cuite paint, and in the second water-soluble bag that the first pouch of whole coating can be placed on the delayed release water-solubility membrane comprising present disclosure or pouch.This scleroma pied-de-cuite coating is not preferably applied directly to SYNTHETIC OPTICAL WHITNER lozenge or composition due to the reactivity of the increase of the oxygenant in SYNTHETIC OPTICAL WHITNER material under the high temperature used with melting sugar.The suitable scleroma pied-de-cuite coating of present disclosure can comprise the mixture of granulated sugar, maize treacle and water.Scleroma pied-de-cuite coating can comprise the granulated sugar of weight ratio in following scope and maize treacle: about 5:1-is about 1:5, about 1:4-and is about 4:1, about 1:3-and is about 3:1, about 1:2-and is about 2:1, about 1:1, about 1:0.5 and/or about 1:0.1.In some embodiments, can manufacture not containing the application of mixture of maize treacle.Such as, scleroma pied-de-cuite coating is by mixing the solution of granulated sugar, maize treacle and water and subsequently solution being heated to 150 DEG C, and the water-soluble pouch or the bag that then soak encapsulating SYNTHETIC OPTICAL WHITNER are used in the sugar soln of melting.

As mentioned above, pouch can be many compartments.The pouch of present disclosure can include but not limited to that light-duty and heavy duty liquid detergent composition, the second pouch being generally used for the useful composition of detergent gels and other laundry additives of doing washing or compartment combinationally use with comprising.Second pouch or compartment therefore, it is possible to can discharge this pouch or compartment component by any film manufacture comprising the fluoropolymer resin that can easily be dissolved in the water of 40 DEG C before the pouch or compartment that comprise delayed release film discharge the component be encapsulated in wherein.The resin being applicable to the water-solubility membrane of the second pouch or compartment includes but not limited to modified polyvinyl alcohol; Polyacrylic ester; Water-soluble acrylic ester multipolymer; Poly-aminopropyl sulfonic acid and salt thereof; Poly-methylene-succinic acid and salt thereof; Polyacrylamide; Polyvinylpyrolidone (PVP); Amylopectin; Cellulosics, includes but not limited to carboxymethyl cellulose and HYDROXY PROPYL METHYLCELLULOSE; Water-soluble natural polymer, includes but not limited to guar gum, xanthan gum, carrageenin and starch; Water soluble polymer derivative, includes but not limited to treated starch, comprises ethoxylated starches and hydroxypropyl starch; Poly-(acrylamido-2-methyl propane sulfonic acid sodium); Poly-monomethyl maleate and salt thereof, its multipolymer and aforementioned in any each other and/or with the combination of PVOH.Certainly, the water-solubility membrane forming the second pouch or assembly can comprise such as to be applicable to other optional additive components of the amount of their desired use, include but not limited to softening agent, tensio-active agent, emulsifying agent, filler, extender, anti-hard caking agent, release agent, defoamer, membrane-forming agent and other functional components, as in this article about described by delayed release film.

Composition for pouch of the present invention can take the form of liquid, solid or powder.Liquid composition can comprise solid.Solid can comprise powder or coacervate, such as micro-capsule, bead, bar or one or more pearly-lustre balls or its mixture.Such solid key element can provide process benefit: thoroughly washing or as pre-treatment, delay or continuous release assembly; In addition or for the election, it can provide effect attractive in appearance.

In the pouch comprising laundry, laundry additive and/or fabric intensifier composition, described composition can comprise in some non-limiting ingredient lists one or more: fabric nursing is benefited reagent; Detergency enzymes; Deposition aid; Rheology modifier; Washing assistant; Organic bleaches; Bleach precursor; SYNTHETIC OPTICAL WHITNER synergistic agent; Bleach catalysts; Spices and/or perfume microcapsules (for example, see US5,137,646); The zeolite of carried perfume; Starch encapsulation (starchencapsulatedaccord); Polyglycerol ester; Whitening agent; Pearling agent; Enzyme stabilising system; Comprise the scavenging agent of the laking agent of anionic dyestuff, the complexing agent of anion surfactant and composition thereof; White dyes or fluorescent agent; Include but not limited to the polymkeric substance of soil release polymer and/or soil suspension polymer; Dispersion agent; Defoamer; Non-aqueous solvent; Lipid acid; Suds suppressor, such as silicone foam inhibitors (see No. 2003/0060390A1, U.S.'s publication, 65-77 page); Cationic starch (see: US2004/0204337A1 and US2007/0219111A1); Scum Dispersants (see: US2003/0126282A1,89-90 page); Dyestuff; Tinting material; Opacifying agent; Antioxidant; Hydrotrote, such as tosylate, cumene sulfonate and naphthalenesulfonate; Look grain; Painted bead, ball or extrudate; Clay softening agent.Any one or more in these compositions is also described in European Patent Application No. 09161692.0 (submission on June 2nd, 2009), No. 2003/0139312A1, U.S.'s publication (submission on May 11st, 2000) and No. 61/229981, U.S. Patent application (submission on July 30th, 2009), and it is transferred the possession of separately and gives Procter & GambleCompany.In addition or for the election, described composition can comprise tensio-active agent and/or solvent system, it is as described below separately.

Described detergent composition can comprise the tensio-active agent of such as about 1 % by weight-80 % by weight.The detersive surfactant utilized can be negatively charged ion, nonionic, zwitter-ion, both sexes or cationic or can comprise the compatibility mixture of these types.In a class embodiment, tensio-active agent is selected from negatively charged ion, nonionic and cats product and composition thereof.Described composition can substantially containing beet alkali surface activator.The example of spendable detergent surfactant is described in United States Patent (USP) 3,664,961,3,919,678,4,222,905 and 4,239, in 659 herein.In another kind of embodiment, tensio-active agent is selected from anion surfactant, nonionogenic tenside and combination thereof.

Useful anion surfactant itself can have number of different types.Such as, the water-soluble salt of higher fatty acid, i.e. " soap ", for can be used for the anion surfactant in composition herein.This comprises alkali metal soap, such as, comprise about 8-about 24 carbon atoms and the sodium of the higher fatty acid of preferred about 12-about 18 carbon atoms, potassium, ammonium and alkylammonium salt.Soap manufactures by the Directly saponification of grease or the neutralization of free fatty acids.Specific usefully derived from sodium and the sylvite of the mixture of the lipid acid of Oleum Cocois and butter, i.e. sodium or potassium butter and coconut soap.

Be adapted at other non-soap anionic surfactant used herein and comprise water-soluble salt, preferably there is the basic metal containing the have an appointment alkyl of 10-about 20 carbon atoms and the organosulfur reaction product of sulfonic acid or sulfate group and ammonium salt in its molecular structure.(comprise the moieties of acyl group at term " alkyl ".) this example being combined into tensio-active agent comprises: a) sodium alkyl sulfate, alkylsurfuric acid potassium and alkylsurfuric acid ammonium, particularly by making higher alcohols (C ₈-C ₁₈) sulphating obtain those, such as by reduction butter or Oleum Cocois glyceryl ester generate those; B) alkyl polyethoxye sodium sulfate, alkyl polyethoxye potassium sulfate and alkyl polyethoxye ammonium sulfate, specifically for wherein alkyl contains 10-22, preferably 12-18 carbon atom and wherein polyethoxye chain contain 1-15, preferred 1-6 ethoxylate part those; And c) sodium alkyl benzene sulfonate and alkyl benzene sulphonate (ABS) potassium, wherein alkyl is containing 9-about 15 carbon atoms of having an appointment, with straight or branched structure, such as, at United States Patent (USP) 2,220,099 and 2, and 477, those types described in 383.Valuable is especially linear alkylbenzene sulfonate, and the average carbon atom number wherein in alkyl is about 11-13, is abbreviated as C ₁₁-C ₁₃lAS.

Nonionogenic tenside can be selected from formula R ₁(OC ₂h ₄) _none or more in those of OH, wherein R ₁for C ₁₀-C ₁₆alkyl or C ₈-C ₁₂alkyl phenyl, and n is 3-about 80.Special expection C ₁₂-C ₁₅the condensation product of alcohol and about 5-about 20 moles of ethylene oxide/mol of alcohol, such as C ₁₂-C ₁₃the condensation product of alcohol and about 6.5 moles of ethylene oxide/mol of alcohol.

Solvent system in the compositions of the present invention can be the solvent system of the mixture containing independent water or organic solvent and water.Organic solvent can comprise 1,2-PD, ethanol, glycerine, dipropylene glycol, methyl propanediol and composition thereof.Also the C of other lower alcohols, such as monoethanolamine and trolamine can be used ₁-C ₄alkanolamine.Such as can there is not solvent system in the anhydrous solid embodiment of present disclosure, but solvent system more generally with about 0.1%-about 98%, preferably at least about in 1%-about 50%, more generally about 5%-about 25% scope level exist.

Organic bleaches can comprise organic peroxide acid, comprises diacyl peroxide and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Described organic peroxide acid can be dibenzoyl peroxide.Diacyl peroxide, particularly dibenzoyl peroxide, the form can with such as about 0.1-about 100 microns, preferably about 0.5-about 30 microns, the more preferably from about particle of the weight-average diameter of 1-about 10 microns exists.In embodiments, at least about 25%-100% or at least about 50% or at least about 75% or be less than 10 microns at least about the particle of 90%, 6 microns are optionally less than.

Other organic bleaches comprise peroxy acid, and specific example is alkyl peroxy acids and aryl peroxy acids.Representative comprises: (a) benzoyl hydroperoxide and cyclosubstituted derivative thereof, such as alkyl peroxy phenylformic acid, also has peroxide-α-naphthoicacid and list to cross naphthoic acid magnesium; (b) aliphatic series or the aliphatic peroxy acids be substituted, such as peroxide lauric acid, peroxystearic acid, ε-phthalimido peroxy caproic acid (phthalimidoperoxycaproicacid) [phthalimido peroxy caproic acid (phthaloiminoperoxyhexanoicacid) (PAP)], adjacent carboxylbenzoyl peroxy caproic acid, N-nonene base amide group peroxide hexanodioic acid and N-nonene base amide group peroxysuccinic acid ester; And (c) aliphatic series and araliphatic peracetic acid; such as 1; 12-diperoxy carboxylic acid, 1; 9-diperoxyazelaic acid, diperoxy sebacic acid, diperoxy brassylic acid, diperoxy phthalic acid, 2-decyl diperoxy fourth-1; 4-diacid, N, N-terephthaloyl two (6-aminoperoxycaproic acid).

The organic peracid precursor of bleaching action is strengthened in the process that bleach-activating agent is clean under can being included in 60 DEG C and lower temperature.Be adapted at the compound providing the aliphatic peroxycarboxylic acid with a preferred 1-10 carbon atom, especially 2-4 carbon atom and/or the peroxybenzoic acid be optionally substituted under bleach-activating agent used herein is included in peroxide hydrolysising condition.Suitable material is with having the O-acyl group and/or N-acyl group of specifying carbonatoms and/or the benzoyl be optionally substituted.Preferred many acylations Alkylenediamine, especially tetra acetyl ethylene diamine (TAED); Acylations pyrrolotriazine derivatives, especially 1,5-diacetyl-2,4-dioxy six hydrogen-1,3,5-triazines (DADHT); Acylations glycoluril, especially tetra-acetylated glycoluril; N-imide, especially N-nonanoyl succimide (NOSI); Acylations phenolsulfonate, especially positive nonanoly acyloxy benzene sulfonate or different nonanoly acyloxy benzene sulfonate (n-or different NOBS); Carboxylic acid anhydride, especially Tetra hydro Phthalic anhydride; Acylations polyvalent alcohol, especially vanay; Glycol diacetate and 2,5-diacetoxy-DHF and trimethylacetyl base citrate (TEAC).

Manganese 7-triazacyclononane and related complex (US-4,246,612, US-A-5,227,084) is comprised for the bleaching catalyst in detergent composition herein; The two pyridine amine of Co, Cu, Mn and Fe and related complex (US-5,114,611); With five amine cobaltous acetates (III) and related complex (US-4,810,410).Another description being adapted at bleaching catalyst used herein being attached to the United States Patent (USP) 6,599 come by reference herein, can be seen in No. 871.

The washing assistant being applicable to detergent composition as herein described comprises water soluble detergency promoter, comprise Citrate trianion, carbonate, silicate and polyphosphate, the mixed sodium of such as tripoly phosphate sodium STPP and tripoly phosphate sodium STPP hexahydrate, Potassium tripolyphosphate and tri-polyphosphate and sylvite.

The enzyme be applicable in detergent composition as herein described comprises bacterium and fungal cellulase, comprises CAREZYME and CELLUZYME (NovoNordiskA/S); Peroxidase; Lipase, comprises AMANO-P (AmanoPharmaceuticalCo.), M1LIPASE and LIPOMAX (Gist-Brocades), and LIPOLASE and LIPOLASEULTRA (Novo); Keratanase; Proteolytic enzyme, comprises ESPERASE, ALCALASE, DURAZYM and SAVINASE (Novo), and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (Gist-Brocades); And amylase, comprise PURAFECTOXAM (Genencor), and TERMAMYL, BAN, FUNGAMYL, DURAMYL and NATALASE (Novo); Polygalacturonase; And composition thereof.Enzyme can add as spherolite, particle or agglomerated thing in the level of the cleaning compositions of the pure enzyme of about 0.0001%-about 2 % by weight in this article usually.

The froth suppressor being adapted at using in detergent composition as herein described comprises the nonionogenic tenside with low cloud point." cloud point " used herein be nonionogenic tenside know character, its solvability being tensio-active agent is the result of step-down along with temperature increase, the temperature that can be observed the outward appearance of second-phase is called as " cloud point " (see VanNostrand ' sScientificEncyclopedia, 4th edition, 366th page, (1968))." low cloud point " used herein nonionogenic tenside is defined as to have and is less than 30 DEG C, is preferably less than about 20 DEG C and is even more preferably less than about 10 DEG C and is most preferably less than the nonionic surfactant system of the cloud point of about 7.5 DEG C.Low cloud point non-ionic surfactants can comprise Nonionic alkoxylated tensio-active agent, particularly derived from the ethoxylate of primary alconol; Block polymer inverse with polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO).Further, this kind of low cloud point non-ionic surfactants can comprise such as ethoxylated-propoxylated alcohol (such as, BASF and epoxy-capped poly-(alkoxylate) alcohol (such as, BASF SLF18) sLF18B series non-ionic surfactants, as such as at US-A-5,576, described in 281).

Comprise for other suitable ingredients in detergent composition as herein described and there is anti-redeposition, soil release or the clean polymkeric substance of other decontamination character.Anti-redeposition polymkeric substance used herein comprises containing acrylic acid polymkeric substance, such as SOKALANPA30, PA20, PA15, PA10 and SOKALANCP10 (BASFGmbH); ACUSOL45N, 480N, 460N (RohmandHaas); Vinylformic acid/maleic acid, such as SOKALANCP5 and acrylic acid series/Sipacril 2739OF.The soil release polymer used in this article comprises alkyl and hydroxy alkyl cellulose (US-A-4,000,093), the nonionic and anionic polymer and composition thereof of polyoxyethylene, polyoxypropylene and multipolymer thereof and the terephthalate based on ethylene glycol, propylene glycol.

Heavy metal chelant and crystal growth inhibitor are also suitable in washing composition, such as with diethylenetriamine five (methene phosphonate ester), ethylenediamine tetraacetic (methene phosphonate ester), hexanediamine four (methene phosphonate ester), ethylene phosphoric acid ester, the hydroxy-ethylene-1 of its salt and free acid form, 1-bisphosphonates, nitrilotriacetate, ethylenediamine tetraacetate, quadrol-N, N'-bis-succinate.

What be applicable to detergent composition as herein described also has corrosion inhibitor, such as organic silver coating agent (particularly paraffin, such as WINOG70, by Wintershall, Salzbergen, Germany sells), Mn (II) compound, particularly Mn (II) salt of nitrogenous corrosion inhibitor compound (such as, benzotriazole and benzoglyoxaline-see GB-A-1137741) and organic ligand.

Enzyme stabilizers is comprised, such as calcium ion, boric acid and propylene glycol for other suitable ingredients in detergent composition herein.

Suitable rinsing additive is known in the art.Business rinse aid for dish washing is generally low bubble poly alkyl alcohol ethylene glycol/polypropylene glycol ether, solubilizing agent (such as, isopropyl sulfonic acid ester), organic acid (such as, citric acid) and solvent (such as, ethanol).The function of this kind of rinse aid is the interfacial tension affecting water, can discharge in this way, thus do not leave water droplet, striped or film from the rinsed surfaces of thin interior poly-form membrane after drying treatment subsequently.The composition of rinse aid and test its performance the summary of method by W.Schirmer etc. at Tens.Surf.Det.28, provide in 313 (1991).The European patent 0197434B1 of Henkel describes containing the rinse aid of mixed ether as tensio-active agent.Also expect the rinsing additive of such as fabric softener etc. and its be applicable to being encapsulated in the film according to disclosure herein.

In one embodiment, pouch or bag can comprise two or more assembly, wherein comprise the first pouch of the water-solubility membrane of present disclosure or compartment comprises alkaline reagents and the second pouch or compartment can comprise liquid laundry detergent.The limiting examples of liquid laundry detergent can comprise the composition presented in table 1 below.

Table 1

¹suitable LAS also comprises the alkyl constructed with straight chain of about 9-about 15 carbon atoms.

In the paragraph of following coding, other embodiments are described.

1. one kind comprises the water-soluble bag of the first sealed compartments of accommodation first composition, described first sealed compartments comprises the wall of water-solubility membrane, and described water-solubility membrane comprises polyvinyl alcohol (PVOH) and acrylate resin and described first composition comprises alkaline reagents.

2. the water-soluble bag of paragraph 1, wherein said polyvinyl alcohol and acrylate resin are the multipolymer of polyvinyl alcohol and methyl acrylate.

3. the water-soluble bag of paragraph 2, wherein said methyl acrylate forms the described multipolymer of about 2 % by mole of-Yue 10 % by mole.

4. the water-soluble bag of paragraph 2, wherein said methyl acrylate forms the described multipolymer of about 5 % by mole.

5. the water-soluble bag of arbitrary section in paragraph 2-4, wherein said multipolymer has suitable viscosity and described water-solubility membrane has suitable thickness, thus provides the deliquescent required delay of described film in the water with described selected temperature be dissolved completely in the water of selected temperature at described film before.

6. the water-soluble bag of arbitrary section in aforementioned paragraphs, wherein, as by bleach-compatible method A measure, keep complete at least 3 minutes when described water-solubility membrane is in the water being immersed in the temperature being heated to about 40 DEG C, and after this dissolved completely in 55 minutes.

7. the water-soluble bag of arbitrary section in aforementioned paragraphs, the thickness of wherein said water-solubility membrane is in about 3 mil-Yue 6 mil (about 0.076mm-is about 0.15mm) scopes.

8. the water-soluble bag of arbitrary section in aforementioned paragraphs, wherein said PVOH multipolymer viscosity is about within the scope of 40cPs at about 8cPs-.

9. the water-soluble bag of arbitrary section in aforementioned paragraphs, wherein, based on the total weight of described film, described PVOH and methacrylate resin form the described film of about 35-about 90 % by weight.

10. the water-soluble bag of arbitrary section in aforementioned paragraphs, it also comprises every 100 parts of PVOH copolymer resins and is about the softening agent that 10-is about 50phr.

The water-soluble bag of 11. paragraphs 10, wherein said softening agent comprises and is selected from Sorbitol Powder, glycerine, two glycerine, propylene glycol, ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, the polyoxyethylene glycol up to MW400,2-methyl isophthalic acid, the material of ammediol, lactic acid, glyceryl monoacetate, vanay, triethyl citrate, 1,3 butylene glycol, TriMethylolPropane(TMP) (TMP), polyether-tribasic alcohol and combination thereof.

The water-soluble bag of arbitrary section in 12. aforementioned paragraphs, also comprises the tensio-active agent that every 100 parts of PVOH copolymer resins are less than about 2phr.

The water-soluble bag of 13. paragraphs 12, wherein said tensio-active agent comprises and is selected from dialkyl sulphosuccinate, the Lactated fatty acid ester of glycerine and propylene glycol, lipid acid lactoyl ester, sodium alkyl sulfate, polysorbate20, polysorbate60, polysorbate65, polysorbate80, alkyl polyglycol ether, Yelkin TTS, the acetylated fatty acid esters of glycerine and propylene glycol, Sodium Lauryl Sulphate BP/USP, the acetylize ester of lipid acid, mnyristoyl dimethyl amine, trimethylammonium ox ester alkyl ammonium chloride, quaternary ammonium compound, the material of its salt and aforesaid any combination.

The water-soluble bag of arbitrary section in 14. aforementioned paragraphs, also comprise the second sealed compartments, described second sealed compartments holds the second composition, and wherein said first sealed compartments and described second sealed compartments optionally link near partition wall.

The water-soluble bag of arbitrary section in 15. aforementioned paragraphs, wherein said first composition and described second composition are for being selected from: liquid, liquid; Liquid, powder; With the combination of the composition of powder, powder.

The water-soluble bag of arbitrary section in 16. aforementioned paragraphs, wherein said alkaline reagents comprises inorganic bleaching agents.

The water-soluble bag of 17. paragraphs 16, wherein said inorganic bleaching agents comprises sodium carbonate, SPC-D or its combination.

The water-soluble bag of arbitrary section in 18. aforementioned paragraphs, the coating material coating comprising polyoxyethylene glycol of wherein said alkaline reagents.

The water-soluble bag of 19. paragraphs 18, wherein said coating has the thickness in about 20 mil-Yue 150 mil (about 0.5mm-is about 3.8mm) scopes.

The water-soluble bag of 20. paragraphs 18 or 19, wherein, as by measured by bleach-compatible method A, keeps complete at least 8 minutes when described first sealed compartments is in the water being immersed in the temperature being heated to about 40 DEG C.

The water-soluble bag of arbitrary section in 21. paragraph 1-17, wherein said alkaline reagents is encapsulated in the second bag, and described second bag scleroma pied-de-cuite paint.

The water-soluble bag of 22. paragraphs 21, wherein said scleroma pied-de-cuite coating comprises the mixture of granulated sugar and maize treacle.

The water-soluble bag of 23. paragraphs 21 or 22, wherein said scleroma pied-de-cuite coating comprises granulated sugar and maize treacle to be about the weight ratio within the scope of 1:5 at about 5:1-.

The dissolving of 24. 1 kinds of manufacturing delays basic component wherein in the hot water of selected temperature also postpones the method for the bag of its release, and it comprises:

Preparation comprises the bag of sealed compartments holding alkaline compositions, and described sealed compartments is by the water-solubility membrane manufacture of multipolymer comprising polyvinyl alcohol (PVOH) and methyl acrylate;

Select in described multipolymer methyl acrylate % by mole, the viscosity of described multipolymer and the thickness of described film is with deliquescent requiredly postponing of providing described film in the hot water of described selected temperature before dissolving completely in the hot water of described selected temperature at described film.

25. 1 kinds of water-soluble bags, it comprises: the first sealed compartments holding the first composition, described first composition comprises the alkaline reagents of the mixture comprising sodium carbonate and SPC-D, described first sealed compartments comprises containing comprising the vinyl alcohol (PVOH) of about 5 % by mole of methyl acrylates and methacrylate resin and having the water-solubility membrane of the thickness of about 3 mil-Yue 6 mils (about 0.076mm-is about 0.15mm), and described bag also comprises the second sealed compartments of accommodation second composition, wherein said first sealed compartments and described second sealed compartments optionally link near partition wall, wherein said second composition comprises laundry additive and wherein as by first composition as described in release at least 3 minutes after being immersed in the water being heated to about 40 DEG C of the first sealed compartments as described in measured by bleach-compatible method A, and the water-solubility membrane of described first seal assembly dissolved completely in 55 minutes.

Embodiment

the mensuration of bleach-compatible method A (method A)

Little 1:1 (% by weight) sodium carbonate of nominal 5 mil (127 μm) water-solubility membrane pouch 5.8g and the 10g compressing tablet of SPC-D mixed powder or same material are filled and sealed.SYNTHETIC OPTICAL WHITNER lozenge can comprise the stearic acid as tackiness agent and manufacture by compress technique well-known to those having ordinary skill in the art.Chlorinated lime material is buied from SolvayChemicals.This pouch uses 0.5 inch of (1.3cm) metal cylinder mould of ethenoid resin coating fastening and to be immersed in the 600ml beaker containing 500ml40 DEG C of deionized water and to stir.Comprise the metal cylinder mould of pouch in submergence before, water is made to be stabilized to pH7.After by pouch submergence, use the pH of pH probe monitoring water and per minute record, until reach the pH of 9.5 or higher, or until 20 minutes in the past.Observe and record integrity and the solubility behavior of pouch.Ideal behavior in 40 DEG C of water is by starting from test (submergence pouch) sharply to increase to mark via discharging the pH that active material causes from pouch when about 9-12 minute.This ideal behavior corresponds in commercially available automatization washing machine cycles, uses 40 DEG C of washing water actives hang-over n.s of nominal to be about 15-20 minute.

the mensuration of bleach-compatible method B (method B)

Bleaching consistency service routine Koch/Bunt (cotton/painted) or equivalent test in SIEMENS board S16-79 washing machine of the water-soluble bag prepared by water-solubility membrane.SIEMENS board S16-79 automatic washing machine has 65 liters of drum capacities and variable thermal creep stress.Test sample as prepared above as described in bleach-compatible method A.The temperature of washing water is 20 DEG C, 40 DEG C or 60 DEG C.Water hardness measuring is 250ppmCaCO ₃(14 ° of d, the Deutschland hardness number of degrees).Wash load is 3kg, is made up of 2 coverlets (1.5x1.5mISO2267), 4 pillowcases (0.8x0.8mISO2267) and 3 diablement fort towels bleached.The dissolution time of method B corresponds to as by reaching the time of the pH of 9.5 or higher measured by pH probe.Ideal behavior sharply increases to mark to use nominal 40 DEG C of washing water to discharge from pouch the pH caused via active material at about 15-20 minute within the commercially available automatic washing machine cycle.

the mensuration (MSTM205) of film solubility characteristics

Film solubleness is measured by MONOSOL test method 205 (MSTM205), and it is open with reference to Fig. 1-3 herein.

MSTM205

Equipment and material:

600mL beaker 12

Magnetic stirring apparatus 14 (Labline model 1250 or equivalent)

Magnetic stirring bar 16 (5cm)

Thermometer (0-100 DEG C, ± 1 DEG C)

Template, stainless steel (3.8cm × 3.2cm)

Timing register (0-300 second, be accurate to immediate second)

Polaroid 35mm sheet folder 20 (or equivalents)

MONOSOL35mm sheet folder clamper 25 (or equivalent, see Fig. 1)

Distilled water

Test sample:

1. use Stainless Molding Board to cut three test sample (that is, 3.8cm × 3.2cm sample) from membrane sample.If cut from film coiled material, the web area that sample evenly should separate along the transverse direction of coiled material is cut.

2. in independent 35mm sheet folder 20, pin each sample.

3. fill beaker 12 with 500mL distilled water.Use thermometer measure water temperature, and if need, then heating or water coolant with holding temperature at 40 DEG C (about 104 ℉).

4. mark the height of water column.Magnetic stirring apparatus 14 is placed on the base 27 of clamper 25.Be placed on by beaker 12 on magnetic stirring apparatus 14, be added in beaker 12 by magnetic stirring bar 16, open agitator 14, and regulate stirring velocity until produce eddy current, it is about 1/5th of water colunm height.Mark eddy current depth.

5. be fastened on 35mm sheet folder 20 (Fig. 1) in the spring pinchcock 26 of MONOSOL35mm sheet folder clamper 25, make sheet press from both sides long end 21 and the plane-parallel of 20, illustrated by fig. 2.The depth adjuster 28 of clamper 25 should be set, thus when dripping, the end of clip 26 will below water surface 0.6cm.One of short side 23 of sheet folder 20 should be close to the side of beaker 12, and opposite side to be directly placed in stirring rod 16 in the heart, makes film surface perpendicular to the flowing of water, as illustrated in figure 3.

6., in once motion, fastening slide plate and clip to be dropped in water and to open timing register.When film splits off, there is disintegration.When all visible films are from the release of sheet folder, cause neatly to go out, continue the dissolving of the undissolved membrane-bound fragment of monitoring simultaneously.Occur to dissolve when all membrane-bound fragments are no longer visible and solution change clarification.

Data logging:

Result will comprise following:

Complete sample survey;

Single and average disintegration and dissolution time; With

In the water temperature of its lower test sample.

Obtain the consoluet time (second).

embodiment 1: bleach-compatible

Be used in the composition identified in table and prepare water-solubility membrane with shown amount (phr).The water-solubility membrane that 5 mils (127 μm) are thick is cast according to prescription 1, and tests dissolution characteristics according to MSTM205 as above.Subsequently film be configured as pouch and the sodium carbonate of 5.8g1:1 (% by weight) and the mixture of SPC-D be encapsulated in pouch and pouch is sealed.The bleaching consistency of pouch measures according to bleach-compatible method A and bleach-compatible method B.Film according to embodiment 1 illustrates, as measured by method A, is being immersed in bleaching component release after 3 minutes in the water being heated to 40 DEG C, and as measured by method B, is being immersed in bleaching component release after 9 minutes in the water being heated to 40 DEG C.

Embodiment 1 illustrates and can be dissolved in completely in the water being heated to 40 DEG C according to the film of present disclosure.Embodiment 1 further illustrates can provide delayed release as the alkali content being measured 3 minutes by method A by the pouch of the film manufacture of present disclosure, and it corresponds to the delayed release as being determined in washing machine 9 minutes by method B.

the solubility behavior of the PVOH homopolymer of comparing embodiment 2. complete hydrolysis

Be used in the composition identified in table and prepare water-solubility membrane with shown amount (phr).The thick water-solubility membrane of 5 mils (127 μm) is cast according to prescription 1,2 and 4, is configured as pouch and is encapsulated in by 1:1 (% by weight) mixture of the sodium carbonate of 5.8g and SPC-D in pouch and is sealed by pouch.The pH testing pouch according to method A as above postpones.

Comparing embodiment 2 illustrates that PVOH homopolymer is not suitable for needing good film workability and the application of both dissolvings completely at 40 DEG C.Low viscosity (6cPs) the film explanation of being cast by film prescription 2 is dissolved sooner needed at 40 DEG C, but sizable variability instruction PVOH resin is in transition region.Film has different molecular-weight average (and therefore different viscosity) according to manufacturer, produce different dissolving properties.Therefore, in observed transition region (about 6cPs), PVOH resin can show too soon or too slow dissolving based on small manufacturer's process variations.Along with the viscosity of water soluble resin increases, such as film is cast (30cPs) by film prescription 4, and gained film illustrates and do not dissolve at 40 DEG C.The film cast by the film prescription 3 of the viscosity with 10cPs also will not dissolve, and therefore can not show the delayed release in the water of the temperature being heated to 40 DEG C.

comparing embodiment 3. replaces the solubility behavior of resin

Be used in the composition identified in table and prepare water-solubility membrane with shown amount (phr).The water-solubility membrane that 5 mils (127 μm) are thick is cast according to prescription 6-10.Subsequently film be configured as pouch and the sodium carbonate of 5.8g1:1 (% by weight) and the mixture of SPC-D be encapsulated in each pouch and pouch is sealed.The bleaching consistency of pouch is tested subsequently according to method A.

Comparing embodiment 3 illustrates the PVOH homopolymer (5 and 6) with medium degree of hydrolysis, the PVOH homopolymer (9) with the complete hydrolysis of the viscosity being less than 5cPs, have the PVOH homopolymer (10) of the complete hydrolysis of the viscosity being greater than 5cPs and comprise the bleaching consistency of modification PVOH resin (7 and 8) of methyl acrylate of the amount being less than 5 % by mole.The PVOH homopolymer (6) that comparing embodiment 3 display has a medium degree of hydrolysis shows not enough solvability and such as not dissolving in 55 minutes that need or shorter time completely for washing machine application.The film cast by the prescription 5 containing the PVOH homopolymer with medium degree of hydrolysis also will show not enough solvability and such as can not dissolving in 55 minutes that need or shorter time completely for washing machine application.Comparing embodiment 3 shows further, expected as based on the dissolubility data from MSTM205, the PVOH homopolymer (9) with the complete hydrolysis of the viscosity being less than 5cPs be heated to 40 DEG C temperature water in be easy to very much dissolve and disintegration, the inclusion of release pouch.Similarly, as using the solubility test of MSTM205 to expect, the PVOH homopolymer (10) with the complete hydrolysis of the viscosity being greater than 5cPs shows not enough solvability and does not even discharge pouch inclusion in the water of temperature being heated to 40 DEG C.Finally, the film that comparing embodiment 3 further illustrates the modification PVOH resin of the methyl acrylate comprising the amount being less than 5 % by mole shows not enough solvability and do not dissolve (7 and 8) completely in 55 minute or shorter time.In addition, the pouch manufactured by film prescription 7 does not even discharge pouch inclusion in the water of temperature being heated to 40 DEG C yet.

embodiment 4: coat condensation material or other PVOH internal layer, polyethylene oxide, carboxymethyl cellulose are coated with material, PEG, sugar.

Water-solubility membrane is according to the preparation preparation described for film preparation 1 above.5 mils (127 μm) water-solubility membrane cast according to film prescription 1 and with the film according to film prescription 1 of 3 mils (76 μm) or the prescription 12 (12) of 3 mils (76 μm) laminated and be configured as pouch.The laminate film (12) with the prescription 12 of the thickness of 3 mils (76 μm) by comprise 100phr the viscosity with 12cPs and be greater than 95% the PVOH resin comprising 4 % by mole of aminopropyl sodium sulfonates of degree of hydrolysis, 26.24phr softening agent, 0.53phr tensio-active agent, 0.03phr defoamer, 1.33phr filler, 2.67phr starch, 0.67phr lubricants/release agents and 0.27phr stablizer water soluble mixt cast.The sodium carbonate of pouch 5.8g and 1:1 (% by weight) mixture of SPC-D are filled, and heat-sealing is also tested according to method A.Contrast pouch (11) has the some A time of about 8 minutes.The pouch (12) of prescription 12 has the some A time of about 5 minutes.Therefore, the pouch (11) of embodiment 4 and (12) illustrate according to pouch of the present invention with have more the laminated hang-over n. that do not cause pouch inclusion of ionic film as the film of prescription 12.The thickness increase that the pouch (11) of embodiment 4 further illustrates water-solubility membrane causes dissolution time to increase, and the hang-over n. of therefore pouch inclusion.Pouch (11) (nominal 8 mil thick) has the some A time of about 8 minutes, and the pouch with the same film (embodiment 2, prescription 1) of the thickness of 5 mils has the some A time of about 3.5 minutes.

The water-solubility membrane of the present disclosure according to film prescription 1 of 5 mils (127 μm) is by the PVOH resin-coating with the PVOH homopolymer of the medium hydrolysis of the viscosity of 29cPs according to film prescription 6 in example 2 of 3 mils (76 μm) and be configured as pouch (13).Filled by 1:1 (% by weight) mixture of the sodium carbonate of pouch 5.8g and SPC-D, heat-sealing is also tested according to method A.Water-solubility membrane does not dissolve completely in 55 minutes or shorter time, and explanation PVOH homopolymer resin applies water-solubility membrane of the present invention and is not suitable for delayed release laundry applications thus.

Using the 10g compressing tablet Dow ' sN-80PolyOx material (nonionic of 1:1 (% by weight) moistening of mixture had as the stearic sodium carbonate of tackiness agent and SPC-D, high molecular weight water-soluble gathers (oxyethane) polymkeric substance, and at 25 DEG C, for 5% solution, range of viscosities is 65-115mPAs) powder coated.Allow coating dry and subsequently lozenge be heat sealed in the thick water-soluble pouch according to film prescription 1 (14) of 5 mils (127 μm).Pouch is tested subsequently according to method A.Find that PolyOx coating efficiency in the too early alkalization providing the consistency of enhancing and reduction water is low.With the lozenge of PolyOx coating, the inconsistent results owing to the powder properties of PolyOx coating is described.Because PolyOx non-melt is processed, so first lozenge to be soaked the adhesivity improving PolyOx coating.This wet processes does not meet needs owing to causing the activation of bleaching compounds.The SYNTHETIC OPTICAL WHITNER of activation causes between the shelf lives (time that is, before purchase on store shelf) at the water-soluble middle formation pin hole containing its water-soluble pouch.Pin hole is formed and causes the delayed release character of film to reduce.In addition, the powder properties of PolyOx produces difference and stores integrity (powder coating can be broken into the fragment of bleaching lozenge/wipe from bleaching lozenge), and this causes inconsistent delayed release character further.

Using 10g compressing tablet Cekol300 carboxymethyl cellulose (CMC) powder coated of 1:1 (% by weight) moistening of mixture had as the stearic sodium carbonate of tackiness agent and SPC-D.Cekol300 has the viscosity of 200-400cPs and the substitution value of 0.60-0.95.Allow coating dry and subsequently lozenge be heat sealed in the thick water-soluble pouch according to film prescription 1 (15) of 5 mils (127 μm).Pouch is tested subsequently according to method A.Find that CMC coating is not enough for this application solvability.

The water-solubility membrane with the thickness of 3 mils (76 μm) by comprise 100phr the viscosity with 18cPs and be greater than 99% the PVOH resin comprising 4 % by mole of aminopropyl sodium sulfonates of degree of hydrolysis (that is, complete hydrolysis), 48.78phr softening agent, 6.02phr tensio-active agent, 0.7phr defoamer, 3.7phr filler, 3.41phr starch and 0.2phr stablizer water soluble mixt cast.This film is configured as pouch, fills with the sodium carbonate of 5.8g and 1:1 (% by weight) mixture of SPC-D and seal.Subsequently pouch is dipped in the melting sugar mixture of the water comprising granulated sugar, maize treacle and be heated to 150 DEG C.The ratio of granulated sugar and maize treacle is about 3:1.Allow the cooling of melting sugar.Subsequently pouch to be encapsulated in the thick water-soluble pouch according to film prescription 1 (16) of 5 mils (127 μm) and to measure bleaching consistency according to method A.The bleaching pouch (16) of scleroma pied-de-cuite coating has illustrated good delayed release character, and the some A time is 12 minutes; With good solubility matter.

embodiment 5: the dissolving of alkalescence bleaching lozenge

For dissolution time, 4 kinds of variants of test 10g alkalescence bleaching lozenge.Tested lozenge is the 10g compressing tablet had as the stearic sodium carbonate of tackiness agent and 1:1 (% by weight) mixture of SPC-D.4 kinds of variants of test are: A) be not encapsulated in the uncoated lozenge in pouch; B) the uncoated lozenge in the pouch of the water-solubility membrane comprising film preparation 1 is encapsulated in; C) with the lozenge that the PEG (MW=6000) of 65 mils (1.65mm) applies; And D) be encapsulated in the lozenge that use 65 mil (1.65mm) PEG6000 in the pouch of the water-solubility membrane comprising film preparation 1 applies.Pouch has the water-solubility membrane thickness of about 4.75 mils (120 μm).The pouch of lozenge and encapsulating lozenge is tested according to method A.Result is shown in table and Fig. 4.Fig. 4 illustrates that after being placed in the water at the temperature being in 40 DEG C, not being encapsulated in uncoated lozenge (A) in pouch being less than in 1 minute dissolves.Fig. 4 illustrates that identical lozenge (C) when being encapsulated in water-soluble pouch of the present invention starts release for about 3 minutes after being immersed in the water being heated to 40 DEG C further.In addition, Fig. 4 illustrate be not encapsulated in pouch within about 1 minute being immersed in the water being heated to 40 DEG C after, start to dissolve with the lozenge of PEG6000 coating and apply with PEG6000 and the lozenge (D) be encapsulated in water-soluble pouch of the present invention until pouch is immersed in the water of the temperature being heated to 40 DEG C within least 8 minutes, just starts to make this scale afterwards.These results show, although PEG6000 coating provides little delayed release feature (about 1 minute for lozenge; Lozenge A is to lozenge C), but it is the result that the chemical stability of the pouch when the alkaline material contacts of pouch not with bleaching lozenge strengthens that the delayed release time illustrated by the pouch of encapsulating coating lozenge strengthens (D, 8 minutes 3 minutes of pouch B to the uncoated lozenge of encapsulating).

embodiment 6: stability in storage

Water-solubility membrane is prepared according to film preparation 1.The water-solubility membrane that 5 mils (127 μm) are thick is cast according to prescription 1, be configured as pouch and the 10g lozenge of 1:1 (% by weight) mixture that has as the stearic sodium carbonate of tackiness agent and SPC-D (uncoated, or with 65 mil PEG6000 coatings coatings) be encapsulated in pouch and pouch is sealed.The bleaching consistency of pouch measures according to bleach-compatible method A.Nearly 6 weeks are stored by under pouch around condition (23 DEG C and 35RH) or 38 DEG C and 80% relative humidity.Embodiment 6 illustrates, when storing at the temperature and 80% relative humidity of conditioned disjunction 38 DEG C around, the water-solubility membrane of present disclosure maintained acceptable delayed release overview through 6 weeks.Think, when uncoated SYNTHETIC OPTICAL WHITNER, (namely lactonic ring is hydrolyzed because of the moisture in SYNTHETIC OPTICAL WHITNER will increase the solvability of water-solubility membrane, film is similar to the PVOH of partial hydrolysis), but, bleaching component in the presence of moisture with film reaction to be hydrolyzed film resin, this causes solvability to reduce, and therefore these effects are resisted each other and worked.Therefore, from air moisture can not remarkably influenced film solvability and dissolution time is relatively stable in time.Also think, when the bleaching lozenge applied, any moisture from SYNTHETIC OPTICAL WHITNER all cannot interact with water soluble resin, and therefore water-solubility membrane illustrates the Initial Solubility strengthened.In addition, the film with the bleaching lozenge of coating is more responsive to the moisture from air between the shelf lives, this is because there is not the antagonistic action effect from bleaching lozenge.Therefore, the solvability with the water-solubility membrane of the bleaching lozenge of coating increased more significantly in the shelf lives.But even if solvability increases, the water-solubility membrane with the bleaching lozenge of coating still maintains acceptable delayed release overview.

Aforementioned description only provides in order to clear understanding, and not should be appreciated that unnecessary restriction since then, because modification within the scope of the invention will be apparent for those of ordinary skill in the art.

Run through this specification sheets and following claims, unless the context requires otherwise, otherwise word " comprises (comprise) " and modification as " comprising (comprises) " and " comprising (comprising) " be interpreted as implying comprise as described in the group of integer or step or integer or step, but do not get rid of the group of any other integer or step or integer or step.

Run through this specification sheets, when being described as by composition comprising component or material, unless otherwise described, otherwise contemplated composition also can substantially be formed by any combination of described component or material or is made up of any combination of described component or material.Similarly, when method is described as comprising particular step, unless otherwise described, otherwise expection method also can substantially be made up of any combination of described step or be made up of any combination of described step.The present invention disclosed in illustrative herein suitably can when do not exist herein concrete disclosed any element or step implement.

The enforcement of method disclosed herein and single step thereof can manually and/or by means of the automatization provided by electronics be carried out.Although method is described with reference to particular, those of ordinary skill in the art will easily understand other modes that can use and perform the effect relevant to these methods.Such as, unless otherwise described, otherwise the order of various step can change when not departing from scope or the spirit of described method.In addition, some single steps can combine, omit or be divided into other step more further.

All patents mentioned in this article, publication and reference are all attached to herein all by reference.If at present disclosure with combined patent, conflict between publication and reference, then should be as the criterion with present disclosure.

Claims

2. water-soluble bag as claimed in claim 1, wherein said polyvinyl alcohol and acrylate resin are the multipolymer of polyvinyl alcohol and methyl acrylate.

3. water-soluble bag as claimed in claim 2, wherein said methyl acrylate forms the described multipolymer of about 2 % by mole to about 10 % by mole.

4. water-soluble bag as claimed in claim 2, wherein said methyl acrylate forms the described multipolymer of about 5 % by mole.

5. the water-soluble bag according to any one of claim 2-4, wherein said multipolymer has suitable viscosity and described water-solubility membrane has suitable thickness, thus provides the deliquescent required delay of described film in the water with described selected temperature be dissolved completely in the water of selected temperature at described film before.

6. as water-soluble bag in any one of the preceding claims wherein, wherein, as by bleach-compatible method A measure, keep complete at least 3 minutes when described water-solubility membrane is in the water being immersed in the temperature being heated to about 40 DEG C, and after this dissolved completely in 55 minutes.

7., as water-soluble bag in any one of the preceding claims wherein, the thickness of wherein said water-solubility membrane is in about 3 mil-Yue 6 mil (about 0.076mm-is about 0.15mm) scopes.

8., as water-soluble bag in any one of the preceding claims wherein, wherein said PVOH multipolymer viscosity is about within the scope of 40cPs at about 8cPs-.

9., as water-soluble bag in any one of the preceding claims wherein, wherein, based on the total weight of described film, described PVOH and methacrylate resin form the described film of about 35-about 90 % by weight.

10., as water-soluble bag in any one of the preceding claims wherein, it also comprises every 100 parts of PVOH copolymer resins and is about the softening agent that 10-is about 50phr.

11. water-soluble bags as claimed in claim 10, wherein said softening agent comprises and is selected from Sorbitol Powder, glycerine, two glycerine, propylene glycol, ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, the polyoxyethylene glycol up to MW400,2-methyl isophthalic acid, the material of ammediol, lactic acid, glyceryl monoacetate, vanay, triethyl citrate, 1,3 butylene glycol, TriMethylolPropane(TMP) (TMP), polyether-tribasic alcohol and combination thereof.

12., as water-soluble bag in any one of the preceding claims wherein, also comprise the tensio-active agent that every 100 parts of PVOH copolymer resins are less than about 2phr.

13. water-soluble bags as claimed in claim 12, wherein said tensio-active agent comprises and is selected from dialkyl sulphosuccinate, the Lactated fatty acid ester of glycerine and propylene glycol, lipid acid lactoyl ester, sodium alkyl sulfate, polysorbate20, polysorbate60, polysorbate65, polysorbate80, alkyl polyglycol ether, Yelkin TTS, the acetylated fatty acid esters of glycerine and propylene glycol, Sodium Lauryl Sulphate BP/USP, the acetylize ester of lipid acid, mnyristoyl dimethyl amine, trimethylammonium ox ester alkyl ammonium chloride, quaternary ammonium compound, the material of its salt and aforesaid any combination.

14. as water-soluble bag in any one of the preceding claims wherein, and also comprise the second sealed compartments, described second sealed compartments holds the second composition, and wherein said first sealed compartments and described second sealed compartments optionally link near partition wall.

15. water-soluble bags as claimed in claim 14, wherein said first composition and described second composition are for being selected from: liquid, liquid; Liquid, powder; With the combination of the composition of powder, powder.

16. as water-soluble bag in any one of the preceding claims wherein, and wherein said alkaline reagents comprises inorganic bleaching agents.

17. water-soluble bags as claimed in claim 16, wherein said inorganic bleaching agents comprises sodium carbonate, SPC-D or its combination.

18. as water-soluble bag in any one of the preceding claims wherein, the coating material coating comprising polyoxyethylene glycol of wherein said alkaline reagents.

19. water-soluble bags as claimed in claim 18, wherein said coating has the thickness in the scope of about 20 mil-Yue 150 mils (about 0.5mm-is about 3.8mm).

20. water-soluble bags as described in claim 18 or 19, wherein, as by measured by bleach-compatible method A, keep complete at least 8 minutes when described first sealed compartments is in the water being immersed in the temperature being heated to about 40 DEG C.

21. water-soluble bags according to any one of claim 1-17, wherein said alkaline reagents is encapsulated in the second bag, and described second bag scleroma pied-de-cuite paint.

22. water-soluble bags as claimed in claim 21, wherein said scleroma pied-de-cuite coating comprises the mixture of granulated sugar and maize treacle.

23. water-soluble bags as described in claim 21 or 22, wherein said scleroma pied-de-cuite coating comprises granulated sugar and the maize treacle that about 5:1-is about the weight ratio within the scope of 1:5.

Select in described multipolymer methyl acrylate % by mole, the viscosity of described multipolymer and the thickness of described film, with deliquescent requiredly postponing of providing described film in the hot water of described selected temperature before dissolving completely in the hot water of described selected temperature at described film.

25. 1 kinds of water-soluble bags, it comprises: the first sealed compartments holding the first composition, described first composition comprises the alkaline reagents of the mixture comprising sodium carbonate and SPC-D, described first sealed compartments comprises the water-solubility membrane comprising vinyl alcohol (PVOH) and methacrylate resin, it comprises about 5 % by mole of methyl acrylates, and there is the thickness of about 3 mil-Yue 6 mils (about 0.076mm-is about 0.15mm), and described bag also comprises the second sealed compartments of accommodation second composition, wherein said first sealed compartments and described second sealed compartments optionally link near partition wall, wherein said second composition comprises laundry additive and wherein as by first composition as described in release at least 3 minutes after being immersed in the water being heated to about 40 DEG C of the first sealed compartments as described in measured by bleach-compatible method A, and the water-solubility membrane of described first seal assembly dissolved completely in 55 minutes.